PIERO M.

ARMENANTE
NJIT
Adsorption with
Granular Activated Carbon
(GAC)
PIERO M. ARMENANTE
NJIT
Adsorption Processes Utilizing
Granular Activated Carbon (GAC)
for Wastewater Treatment
In all these processes the wastewater is
contacted with granular activated carbon (GAC)
typically in a semi-batch or continuous operation.
Processes that utilize this type of carbon include:
Fixed-bed or expanded-bed adsorption
Moving-bed adsorption
Fluidized-bed adsorption
PIERO M. ARMENANTE
NJIT
Fixed-Bed and Expanded-Bed
Adsorption Systems
Wastewater
in
Wastewater
out
Wastewater
out
Wastewater
in
Fixed-Bed Expanded-Bed
PIERO M. ARMENANTE
NJIT
Modes of Operation of Fixed-Bed and
Expanded-Bed Systems
Downflow Fixed-bed
Upflow
- Expanded-bed (if the wastewater velocity
expands the bed by about 10% or higher)
- Fixed-bed
PIERO M. ARMENANTE
NJIT
Downflow Fixed-Bed Adsorbers
This is the most common type of adsorption
column for wastewater treatment
These columns must be provided with a system for
the removal of spent carbon and the addition of
fresh or regenerated carbon
Because or their construction and operation
downflow fixed-bed adsorbers also acts as depth
filters for particles that can be contained in the
wastewater
Therefore this adsorption column must also be
provided with facilities for backwashing (including
air scouring, if necessary)
PIERO M. ARMENANTE
NJIT
Typical GAC Contactor
After Metcalf and Eddy, Wastewater Engineering, 1991, p. 316
PIERO M. ARMENANTE
NJIT
Characteristics of Commercial Adsorbers
Height of packing 3 - 9 m (10 - 30 ft)
Particle size 8 - 40 mesh
Hydraulic loading 1.4 - 6.8 L/m
2
s (2 -10 gpm/ft
2
)
Residence time 10 - 60 min (typically 20 -30 min)
Typical carbon
requirements
- pretreatment
- tertiary treatment
(in g carbon/m
3
wastewater)
60 - 200
25 - 50
Operating pressure < 20 KPa/m of bed
After Sundstrom and Klei, Wastewater Treatment, 1979, p. 270 and
Metcalf and Eddy, Wastewater Engineering, 1991, p. 753
PIERO M. ARMENANTE
NJIT
Properties of Commercially Available
Carbons
After Eckenfelder, Industrial Water Pollution Control, 1989, p. 268
PIERO M. ARMENANTE
NJIT
Downflow Fixed-Bed Adsorbers in
Series
Wastewater in
PIERO M. ARMENANTE
NJIT
Downflow Fixed-Bed Adsorbers in
Parallel
Wastewater in
PIERO M. ARMENANTE
NJIT
Granular Activated Carbon Process Flow Diagram
After Corbitt, R. A. 1990, The Standard Handbook of Environmental Engineering,
p. 6.199
Results of Adsorption
Tests on Typical
Industrial Wastewaters
PIERO M. ARMENANTE
NJIT
Upflow Expanded-Bed Adsorbers
In general, most upflow adsorbing columns
operate in the expanded-bed mode
Expanded-bed adsorbers are used when the
wastewater fed to the column contains a
significant fraction of suspended particles
Since the bed is always expanded the column
does not act as a filter for the suspended
particles
PIERO M. ARMENANTE
NJIT
Upflow Fixed-Bed Adsorbers in
Series
Wastewater in
PIERO M. ARMENANTE
NJIT
Moving-Bed Adsorption
Carbon in
Carbon out
Wastewater
out
Wastewater
in
PIERO M. ARMENANTE
NJIT
Fluidized-Bed Adsorption
Wastewater
out
Wastewater
in
PIERO M. ARMENANTE
NJIT
Adsorption Beds as Filter Beds and
Heavy Metal Adsorbers
GAC beds are sometimes used as deep-bed
filters (as well as adsorbers)
the capital cost associated with dual purpose
adsorber-filter beds is typically lower than
separate beds
the regeneration of the adsorptive capacity of
the bed should be followed by the removal of
solids via bed fluidization
most heavy metals are also adsorbed on
activated carbon beds
PIERO M. ARMENANTE
NJIT
Biological Reactions in Adsorption Beds
The presence of organic material in a typical activated
carbon bed coupled with the presence of
microorganisms in the wastewater makes the bed an
ideal breeding ground. This can have both negative
and positive effects:
the microorganisms may contribute to the
breakdown of pollutants adsorbed on the bed, thus
improving its performance
the presence of excessive organic material and the
typical lack of oxygen may result in anaerobic
growth (associate with the potential for odor
generation) and the plugging of the bed due to
excessive growth
PIERO M. ARMENANTE
NJIT
Most Important Design Factors in
Fixed-Bed Adsorption Systems
Particle size
Diameter of column
Flow rate of incoming wastewater (or
residence time)
Height of adsorption bed
Pressure drop
Time required to achieve breakthrough
(Time of exhaustion)
PIERO M. ARMENANTE
NJIT
Analysis of Fixed-Bed
Adsorption Systems
PIERO M. ARMENANTE
NJIT
Steps Involved in Adsorption
As the wastewater moves through a fixed bed of
carbon the pollutant to be adsorbed will move from
the wastewater to the carbon bed. Several steps are
involved in the overall adsorption process of a
single molecule of pollutant:
Mass transfer step. Mass transfer from the bulk
of the wastewater to the surface of the carbon
particle through the boundary layer around the
particle
Diffusion step. Internal diffusion through a pore
Adsorption step. Adsorption on to the surface of
the particle
PIERO M. ARMENANTE
NJIT
Relative Magnitude of the Rates
Involved in Adsorption Process
In most wastewater treatment applications the
overall adsorption process is dominated by mass
transfer, especially intraparticle mass transfer. A
qualitative ranking of the magnitude of the
resistances is:
External interparticle mass transfer step
slow to not-so-slow, depending on the operation
Intraparticle diffusion step typically slow
Adsorption step typically fast
PIERO M. ARMENANTE
NJ IT
External Interparticle
Mass Transfer Film
Intraparticle
Diffusion
Adsorption
Liquid
Bulk
Carbon Particle
Pore
PIERO M. ARMENANTE
NJIT
Effect of Carbon Particle Size on
Pressure Drop and Intraparticle Mass
Transfer
The size of the activated carbon particle has an
opposite impact on the pressure drop across the
bed and the intraparticle diffusion resistance (and
hence on the overall adsorption process)
PIERO M. ARMENANTE
NJIT
Effect of Carbon Particle Size on
Pressure Drop
The effect of particle size, D
p
, on pressure drop,
P, can be determined recalling equations such
as the Ergun Equation for pressure drop in
granular media:
( ) P
L
D
u
p p
L s
+

1
]
1
1

_
,

150
1 175
1
3
2
Re
.

or the Fair-Hatch equation (laminar flow):
( )
P k
L
D
u
p
s

36
1
2
3 2

PIERO M. ARMENANTE
NJIT
Effect of Carbon Particle Size on
Pressure Drop
The pressure drop in a carbon bed is inversely
proportional to the particle size. In particular it is:
P
D
p

1
for turbulent flow through granular media, and:
P
D
p

1
2
for laminar flow in granular media.
PIERO M. ARMENANTE
NJIT
Effect of Carbon Particle Size on
Intraparticle Mass Transfer
As a first approximation the effect of particle size on
the intraparticle mass transfer of pollutant can be
estimated as follows:
pollutant transferred inside the particle
bed volume
pollutant transferred inside the particle
bed volume

D
dC
d r
A
V
D
C
r D
D
C
D D
D
p
p
p p p
p

6 0
0
12
1
2
PIERO M. ARMENANTE
NJIT
Effect of Carbon Particle Size on
Pressure Drop and Diffusion Resistance
Larger carbon
particle size

Smaller carbon
particle size

Smaller pressure
drop

Larger pressure
drop

Smaller mass of
pollutant diffusing
inside the particle
Larger mass of
pollutant diffusing
inside the particle
PIERO M. ARMENANTE
NJIT
Size of Activated Carbon Particles Used
in Fixed-Bed Adsorption
Typically carbon particle sizes between 0.4 and
2.5 mm are used in fixed bed adsorption
applications
This size range results from a practical
compromise between limiting the pressure
drops on one hand and providing adequate
surface area and promote mass transfer for
pollutant adsorption on the other
Larger sizes also minimize losses during
carbon handling and packed bed operation
PIERO M. ARMENANTE
NJIT
Adsorption Zone and Adsorption Wave
In fixed bed adsorption, at any given time the
bed can be divided into three approximate
zones, i.e., the saturated zone
(containing carbon nearly
saturated with the pollutants),
followed by the adsorption
zone (were adsorption actually
takes place), followed by a
zone in which the carbon contains little or no
adsorbed pollutant
The size and location of the three zones within
the bed change with time
Adsorption
Zone
Saturated
Zone
PIERO M. ARMENANTE
NJIT
Adsorption Zone and Adsorption Wave
(continued)
As the wastewater enters the bed it first
encounters the saturated zone in which the
carbon is already nearly saturated with the
pollutant (this is not true for fresh completely
clean beds just being put on line, of course).
Practically no adsorption occurs in the
saturated zone
As more wastewater travels through the bed
the saturated zone expands progressively
through the bed, eventually including it
completely
PIERO M. ARMENANTE
NJIT
Adsorption Zone and Adsorption Wave
(continued)
Pollutant adsorption occurs nearly exclusively
over a portion of the bed called the adsorption
zone, downstream of the saturated zone
The concentration of pollutant in the carbon
varies from near saturation (at the beginning of
the adsorption zone) to near zero (toward the
end of the adsorption zone). Conversely, the
pollutant concentration in the wastewater in
contact (at that time) with the carbon changes
from nearly full load (at the beginning of the
adsorption zone) to nearly zero (at the end)
PIERO M. ARMENANTE
NJIT
Adsorption Zone and Adsorption Wave
(continued)
At any given time the portion of the bed
downstream of the adsorption zone contains
very little adsorbed pollutant since the
wastewater it is in contact with has already
been nearly completely depleted of the
pollutant(s)
As time goes by a greater portion of the bed
becomes saturated with the pollutant and the
adsorption zone moves downstream forming
an adsorption wave
PIERO M. ARMENANTE
NJIT
Breakpoint and Breakthrough Curve
Eventually the forward part of the adsorption
wave reaches the end of the bed. When this
happens the bed begins to release wastewater
having a concentration of pollutant higher than
the desired value (typically 5-10% of the
influent concentration). This point is called the
breakpoint
The corresponding curve of pollutant
concentration in the effluent vs. time is called
the breakthrough curve
PIERO M. ARMENANTE
NJIT
Exhaustion Point and Bed Saturation
Past the breakpoint the pollutant concentration
in the effluent rises rapidly (i.e., the
breakthrough curve is typically steep), until it
reaches an arbitrarily defined exhaustion point
where the column approaches saturation
If more wastewater is passed through the bed
the entire carbon content of the bed becomes
saturated. Then, the wastewater leaving the
bed has, for all practical purposes, the same
concentration of pollutant as the incoming
wastewater
PIERO M. ARMENANTE
NJIT
Breakpoint and Breakthrough Curve
Cumulative Wastewater Volume
C
Adsorption
Zone
C C C C
C
o
C
o
C
o
C
o
B E
Breakpoint
Breakthrough
Curve
Exhaustion
Point
PIERO M. ARMENANTE
NJIT
Concentration of Adsorbate in the
Carbon Along a Fixed-Bed Column
Position Along Fixed-Bed Column
q
Adsorption
Zone
C C C C
C
o
C
o
C
o
C
o
B E
1 2 3 4
1 2 3 4
PIERO M. ARMENANTE
NJIT
Evolution of Concentration Profiles in in the Wastewater Leaving
the Column and in the Carbon Bed as a Function of Time
Cumulative Wastewater Volume
C
Breakpoint
Breakthrough
Curve
Exhaustion
Point
t
1
t
2
t
3
t
4
Position Along Fixed-Bed Column
q
t
1
t
2
t
3
t
4
PIERO M. ARMENANTE
NJIT
Progressive Saturation of Adsorber in
Column as a Function of Time
Position Along
the Column
q q q q
t
F t t
B
t
E
PIERO M. ARMENANTE
NJIT
Typical Breakthrough Curves
After Eckenfelder, Industrial Water Pollution Control, 1989, p. 272
PIERO M. ARMENANTE
NJIT
Shapes of Breakthrough Curves
V
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
C
/
C
o
VB
VE
Short Depth of Adsorption Zone

V
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
C
/
C
o
VB VE
Large Depth of Adsorption Zone
PIERO M. ARMENANTE
NJIT
Analysis of Fixed-Bed Adsorption
Columns
The primary objectives of such an analysis are:
determination of the total (maximum) column
adsorption capacity;
determination of the depth of the adsorption
zone and the shape of the breakthrough curve;
determination of the breakpoint, including the
volume of wastewater that can be treated
before the breakpoint is reached, the time at
which this happens, and the degree of column
saturation at breakpoint.
PIERO M. ARMENANTE
NJIT
Total Column Adsorption Capacity
If the adsorption equilibrium curve is known then
by knowing the volume of the column and its void
fraction, one can calculate the total cumulative
volume of wastewater, V
max
, that could be treated
if the column became completely saturated:
( ) V SL
q
C
SL
q
C
s
So
o
sapp
So
o
max
1
where: S = column cross sectional area
L = height of packing
= void fraction
q
So
= g(C
o
) = value of q in equilibrium with C
o

s
and
s app
= real and apparent density of solid
PIERO M. ARMENANTE
NJIT
Approaches to the Design of
Adsorption Columns
Many different approaches are available. In general,
partial differential equations can be written,
incorporating the different mass transfer and
adsorption mechanisms. Typically these models are
complex and require numerical solutions.
Other models rely on experimental data and the use of
simpler models to interpret them so as to produce
satisfactory designs. These models can be used to
size the column by determining the depth of the
adsorption zone, the shape of the breakthrough curve,
the time at breakpoint and the pollutant removed at
breakpoint.
PIERO M. ARMENANTE
NJIT
Models Examined Here
Three models will be examined here in some
detail:
Simplified Method for Estimation of Fixed-Bed
Adsorption Performance
Design of Adsorption Columns Based on
Capacity of Adsorption Zone (Mass Transfer
Model)
Design of Adsorption Columns Based on Bed
Depth Service Time (BDST) Method (Surface
Reaction Model)
PIERO M. ARMENANTE
NJIT
Simplified Method for the Estimation
of Fixed-Bed Adsorption Performance
Simplifying assumptions:
the pollutant concentration in the effluent
wastewater from the column increases linearly
with time until it reaches the breakpoint value,
C
B
at breakpoint the average concentration of
pollutant in the bed is only a fraction, , of the
saturation value (typically 50%)
the wastewater flow rate to the column is
constant and equal to Q
PIERO M. ARMENANTE
NJIT
Simplified Method for the Estimation
of Fixed-Bed Adsorption Performance
From a mass balance for the pollutant at
breakpoint it is:
M q B q B Qt C
C
Qt C
B so B o
B
B o

_
,

2
where:
M = cumulative mass of pollutant adsorbed at
breakpoint
B = mass of carbon in bed =
s app
S L, and:
q K C
so F o
n

1
PIERO M. ARMENANTE
NJIT
Simplified Method for the Estimation
of Fixed-Bed Adsorption Performance
Hence, the time required to reach breakthrough
is:
t
q B
Q C
C
K C B
Q C
C
B
B
o
B
F o
n
o
B

_
,

_
,

2 2
1

The cumulative volume of wastewater, V

B
, treated
at breakpoint is given by:
V Qt
B B

PIERO M. ARMENANTE
NJIT
Design of Adsorption Columns Based
on Capacity of Adsorption Zone
(Mass Transfer Model)
This model assumes that the adsorption zone has
a constant shape that moves down the column
with time and that the process is controlled by the
mass transfer around the carbon pellets.
PIERO M. ARMENANTE
NJIT
Definitions
L = height of packed bed
t
F
= time required for the adsorption zone to form
t
L
= time required for the fully formed adsorption
zone to move down the length of the column, L,
until the effluent concentration is equal to C
E
t
E
= time required for the effluent concentration to
reach the exhaustion point, C
E
t
A
= time, required for the adsorption zone to
move its own height down the column
PIERO M. ARMENANTE
NJIT
Time Required to Exhaust the Bed
The time, t
E
, required for the effluent concentration to
reach the exhaustion point, C
E
, is equal to the sum of:
the time, t
F
, required for the adsorption zone to
form
the time, t
L
, required for the fully formed
adsorption zone to move down the length of the
column, L, until the effluent concentration is equal
to C
E
Then, it is:
t t t
E F L
+
i.e.:
t t t
L E F

PIERO M. ARMENANTE
NJIT
Time Required to Exhaust the Bed
The time, t
E
, required for the effluent
concentration to reach the exhaustion point, C
E
, is
also equal to:
t
V
Q
V S
Q S
E
E E

where:
V
E
= cumulative wastewater volume passed
through the column during the time interval
0 - t
E
Q = wastewater flow rate
PIERO M. ARMENANTE
NJIT
Time Required for Adsorption Zone
to Move Its Own Height
The time, t
A
, required for the adsorption zone to
move its own height down the column is:
t
V V
Q
A
E B

where:
V
B
= cumulative wastewater volume passed
through the column during the time interval
0 - t
B
t
B
= time required for the effluent concentration to
reach the breakpoint, C
B
PIERO M. ARMENANTE
NJIT
Adsorption Wave Velocity
The velocity, u
A
, of the adsorption zone (equal to
the wave velocity, u
w
) is given by:
u
L
t
L
t t
u
L
t
W
L E F
A
A
A

which can be rearranged to give:
L
L
t
t
t
t t
A A
L
A
E F

where:
L = height of column
L
A
= height of adsorption zone
PIERO M. ARMENANTE
NJIT
Fractional Pollutant Removed in the
Adsorption Zone
If additional wastewater is passed through the
column after the effluent concentration has
reached the breakpoint, C
B
, more pollutant will be
removed until the effluent concentration becomes
equal to C
E
. This extra amount of pollutant is:
( ) m C C dV
o
V
V
B
E

This amount is only a fraction of that which could

be removed if the adsorption zone was not at the
end of the column, in which case it would be:
( ) m C V V
s o E B

PIERO M. ARMENANTE
NJIT
Fractional Pollutant Removed in the
Adsorption Zone
The fractional pollutant removal capacity at the
end of the column, f, is then:
( )
( )
f
m
m
C C dV
C V V
s
o
V
V
o E B
B
E

The fractional pollutant removal capacity, f, can

be determined experimentally by monitoring the
effluent concentration (after the breakpoint) as a
function of the effluent cumulative volume.
PIERO M. ARMENANTE
NJIT
Fractional Pollutant Removed in the
Adsorption Zone
f
m
m
C
C
d
V V
V V
s o
B
E B

_
,

_
,

(
1
0
1
0 0.2 0.4 0.6 0.8 1
(V-V
B
)/(V
E
-V
B
)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
C
/
C
o
C /C
B o
C /C
E o
Experimental
Points
PIERO M. ARMENANTE
NJIT
Pollutant Removed in the Adsorption
Zone: Large f Value (f 1)
C
E
/C
o
C
B
/C
o
Experimental
Points
0 0.2 0.4 0.6 0.8 1
0
0.2
0.4
0.6
0.8
1
0 0.2 0.4 0.6 0.8 1
(V-V
B
)/(V
E
-V
B
)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
C
/
C
o
f = Gray Area
PIERO M. ARMENANTE
NJIT
Pollutant Removed in the Adsorption
Zone: Large f Value (f1)
If f1, then the adsorption zone at the end of the
column already contains a significant amount of the
adsorbate and has the potential for adsorbing very
little extra pollutant.
This implies that, in general, the wastewater
saturates the carbon layer by layer and that the
transition zone from the fully saturated carbon zone
to the unsaturated zone is short. This typically
occurs when the wastewater velocity is low.
This also means that the adsorption zone is quite
short and the time required for its formation is close
to zero.
PIERO M. ARMENANTE
NJIT
Pollutant Removed in the Adsorption
Zone: Small f Value (f0)
0 0.2 0.4 0.6 0.8 1
(V-V
B
)/(V
E
-V
B
)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
C
/
C
o
f = Gray Area
Experimental
Points
C
B
/C
o
C
E
/C
o
PIERO M. ARMENANTE
NJIT
Pollutant Removed in the Adsorption
Zone: Small f Value (f0)
If f0, then the adsorption zone at the end of the
column contains little adsorbate in the carbon. Hence it
has the potential for adsorbing nearly as much as a
similar zone made of fresh carbon.
This implies that, in general, the wastewater does not
saturate the carbon layer by layer, but that the
transition zone from the fully saturated carbon zone to
the unsaturated zone is gradual. This typically occurs
when the wastewater velocity is high.
This also means that the adsorption zone is quite deep
and the time required for its formation is large and
nearly equal to that needed for the adsorption zone to
move a distance equal to its depth.
PIERO M. ARMENANTE
NJIT
Time Required for the Formation of
the Adsorption Zone
As the wastewater first enters a column containing fresh
(or regenerated) activated carbon the adsorption zone is
not established. The time required for the formation of
the adsorption zone can be estimated from:
( ) t f t
F A
1
When f1, the length of the adsorption zone is quite
small and the time for the formation of the adsorption
zone, t
F
, is nearly zero (layer-by-layer buildup);
When f0, the length of the adsorption zone is quite
extended and the time for the formation of the
adsorption zone, t
F
, is significant.
PIERO M. ARMENANTE
NJIT
Height of Adsorption Zone
Recalling that it is:
L
L
t
t
t
t t
A A
L
A
E F

it is possible now to eliminate t

F
from the
expression of the L
A
/L ratio to get:
( )
L
L
t
t
t
t f t
A A
L
A
E A

1
which can also be expressed in terms of the
corresponding cumulative volumes as:
( )
( )
L
L
V V
V f V V
A E B
E E B

1
PIERO M. ARMENANTE
NJIT
Height of Adsorption Zone
The equation:
( )
( )
( )
L
L
V V
V f V V
V
S
V
S
V
S
f
V
S
V
S
A E B
E E B
E B
E E B
'

_
,

1
1
can be use to experimentally determine the height
of the adsorption zone, L
A
, from experimental lab
data (since only the ratios V
i
/S are important).
The experiments should be conducted for the
same value of the ratio Q/S. Then the value of L
A
can be determined provided the height of the test
column (L') is known.
PIERO M. ARMENANTE
NJIT
Interpretation of Experimental Data
A common way to collect information on the
performance of an adsorption column and to
scale up the results consists in
setting up a column as high as
that eventually to be used in
the full scale application, but
of much smaller diameter
Data are then collected by
determining the time at
breakpoint, t
B
, at different
points (ports) along the
column
Port
Port
PIERO M. ARMENANTE
NJIT
Experimental Determination of
the f Value
The f value can be determined experimentally by
obtaining C vs. V data as the adsorption zone
passes through the sampling port. Since V
B
and
V
E
can also be determined with this approach
then f can be calculated from its definition:
( )
( )
f
m
m
C C dV
C V V
s
o
V
V
o E B
B
E

PIERO M. ARMENANTE
NJIT
Degree of Column Saturation at
Breakpoint
The degree of column saturation at breakpoint, ,
is defined as the fraction of column saturation at
breakpoint, i.e.:

Amount of pollutant in column at breakpoint
Maximum theoretical amount of pollutant in column
The value of is within the range 0 - 1, and is
proportional to the degree of utilization of the
activated carbon packing at breakpoint, i.e.,
before the column must be shut down for carbon
replacement or regeneration.
PIERO M. ARMENANTE
NJIT
Degree of Column Saturation at
Breakpoint (continued)
Saturated
Zone
C C
C
o
C
o
B o
Column at
breakpoint
Saturated
column
Adsorption
Zone
( ) ( ) ( ) ( )
( )
( ) ( )

+
M
M
S L L q SL f q
SL q
S L L q SL f q
SL q
S
A s So A s So
s So
A s app So A s app So
s app So
1 1 1
1
1
PIERO M. ARMENANTE
NJIT
Degree of Column Saturation at
Breakpoint (continued)
By simplification one can obtain the following
equation for :
( )
( )

+
M
M
L L L f
L
S
A A
1
i.e.:

M
M
L f L
L
S
A
If f and L
A
have been determined can be
calculated for any column of length L.
PIERO M. ARMENANTE
NJIT
Calculation of Cumulative Pollutant
Removal at Breakpoint
Once is known it is possible to determine the
cumulative amount of pollutant, M, removed by
the time the breakpoint is reached (and the
column must be taken off line):
M M q SL K C SL
S So sapp F o sapp
n

1
where C
o
is the pollutant concentration in the
incoming wastewater.
PIERO M. ARMENANTE
NJIT
Calculation of Breakpoint Time
The breakpoint time, t
B
, can be calculated as:
t
B

cumulative amount of pollutant adsorbed at breakpoint
rate of pollutant fed to column
i.e.:
t
M
QC
B
o

at which time the column must be taken off line.

The cumulative volume of wastewater, V
B
, treated
at breakpoint is given by:
V Qt
B B

PIERO M. ARMENANTE
NJIT
Alternative Determination of the
Adsorption Zone Profile
An alternative method to determine the profile and
length of the adsorption zone (and hence the f
value and L
A
) is to model the adsorption zone as if
it were an independent column operating at
steady state and having a continuous input of
both solid activated carbon and wastewater.
This approach is equivalent to assume that the
frame of reference moves with the adsorption
wave.
PIERO M. ARMENANTE
NJIT
Alternative Determination of the
Adsorption Zone Profile
C
o
C
E
C
B
C=0
C
E
C
B
q
B
q
E
L
L
A
L
A
dZ
Q
Q
q
q
so
q
E
q
B
q=0
PIERO M. ARMENANTE
NJIT
Alternative Determination of the
Adsorption Zone Profile: Mass Balance
In performing a mass balance for such a continuous
column the assumption is made that the incoming
and outgoing streams are nearly in equilibrium (if
they were really in equilibrium the column will be
infinitely high).
This implies that the incoming wastewater (pollutant
concentration: C
o
) encounters a carbon which is
practically saturated with the pollutant at that
concentration (q
So
).
Similarly the wastewater leaving the column contains
practically no pollutant, and so does the fresh
incoming carbon.
PIERO M. ARMENANTE
NJIT
Alternative Determination of the
Adsorption Zone Profile: Mass Balance
A material balance around the entire continuous
column gives:
( ) ( ) Q C Q q
o q So
0 0
where:
Q = wastewater flow rate
Q
P
= carbon flow rate
C
o
= pollutant concentration in incoming
wastewater
q
So
= pollutant concentration in spent carbon
PIERO M. ARMENANTE
NJIT
Alternative Determination of the
Adsorption Zone Profile: Mass Balance
Similarly, a material balance between the bottom
of the column and a generic section gives:
( ) ( ) Q C Q q
q
0 0
Hence, the operating line (mass balance) for the
continuous column is:
C
q
C
q
Q
Q
o
So
q

Remark: the points (C
E
, q
E
) and (C
B
, q
B
) must lie
on the operating line.
PIERO M. ARMENANTE
NJIT
Alternative Determination of the
Adsorption Zone Profile: Mass Balance
q (g solute/g carbon)
C

(
g
/
L
)
Isotherm
Operating Line
Q
q
/Q
q
B
q
E
q
So
C
B
C
E
C
o
C
C*
q
PIERO M. ARMENANTE
NJIT
Alternative Determination of the
Adsorption Zone Profile: Mass Balance
in a Differential Section of the Column
Assuming that external (or external-internal) mass
transfer dominates the overall adsorption
phenomenon a differential balance for the
pollutant in an infinitesimally thin layer of the
column yields:
Rate of pollutant removal from the wastewater =
Rate of pollutant transfer to the carbon
PIERO M. ARMENANTE
NJIT
Alternative Determination of the Adsorption
Zone Profile: Mass Balance in a Differential
Section of the Column
In mathematical terms the previous equation can be
written as:
( )
Q
S
dC u dC K a C C dz
s L
*
K
L
= mass transfer coefficient between the bulk of the
wastewater and the surface of the carbon (m/s)
a = external surface area of carbon particles per unit
bed volume
C* = concentration of pollutant in the wastewater that
would be in equilibrium with the adsorbed
concentration, q
PIERO M. ARMENANTE
NJIT
Alternative Determination of the
Adsorption Zone Profile: Integration
of Mass Balance Equation
Integration of the previous equation yields:
z
u
K a
dC
C C
C C C
s
L
C
C
B E
B

(

'
' '*
for
In addition it is:
L
u
K a
dC
C C
A
s
L
C
C
B
E

(
'
' '*
PIERO M. ARMENANTE
NJIT
Alternative Determination of the
Adsorption Zone Profile: Calculation of f
From the previous equations it is:
z
L
V V
V V
dC
C C
dC
C C
z L V V V
A
B
E B
C
C
C
C A B E
B
B
E

(
< < < <
'
' '*
'
' '*
with and 0
From this equation and recalling that:
f
m
m
C
C
d
V V
V V
s o
B
E B

_
,

_
,

(
1
0
1
the value of f can be calculated knowing only C
B
,
C
E
and the adsorption isotherm.
PIERO M. ARMENANTE
NJIT
Design of Adsorption Columns Based
on Bed Depth Service Time (BDST)
Method (Surface Reaction Model)
This method is based on the used of experimental
data from columns of different depths (or a single
column with ports) and the determination of the
breakthrough curves as a function of time. These
data provide information on the service time for
each bed-depth (from which the name).
Equations can be used to analyze these data to
produce design relationships.
This method is an extension of a surface reaction
model derived by a number of investigators.
PIERO M. ARMENANTE
NJIT
Breakpoint Time vs. Column Length
The breakpoint time for an adsorption column is:
( )
t t t t
B F L A
+
where:
t
F
= time required for the adsorption zone to form
t
L
= time required for the adsorption zone to travel
down the column
t
A
= time required for the adsorption zone to travel
its own height
(compare this with definition of t
E
)
PIERO M. ARMENANTE
NJIT
Breakpoint Time vs. Column Length
(continued)
Recalling that u
W
is the velocity of the adsorption
wave (and hence of the adsorption zone, u
A
) the
previous equation becomes:
t t
L
u
t
B F
W
A
+

_
,

Recalling that ( ) t f t
F A
1 then it is:
( )
t f t
L
u
t
B A
W
A
+ 1
PIERO M. ARMENANTE
NJIT
Breakpoint Time vs. Column Length
(continued)
By rearranging the previous equation one finds:
t
u
L
f L
u
B
W
A
W

1
which implies that the breakpoint time increases
linearly with the length of the column, L.
This also means that a plot of t
B
vs. L (for example
using an experimental column in which L is the
height of the different ports) should give a
straight line.
PIERO M. ARMENANTE
NJIT
Breakpoint Time vs. Column Length
(continued)
The rate of advancement of the saturated zone in
the column is equal to the wave velocity, u
W
. As a
result, each layer of upstream of the adsorption
zone will become progressively saturated as the
adsorption zone moves. Hence a mass balance
for the pollutant gives:
QC q Su
o so s app W

pollutant removed from wastewater = pollutant adsorbed
PIERO M. ARMENANTE
NJIT
Breakpoint Time vs. Column Length
(continued)
The previous equation provides us with an
expression for u
W
:
u
Q
S
C
q
W
o
s app so

which can be used in the equation for t

B
to give:
t
q
u C
L
q f
u C
L
B
s app so
S o
s app so
S o
A


since u
S
= Q/S.
PIERO M. ARMENANTE
NJIT
Breakpoint Time vs. Column Length
(continued)
Finally, experimental data from test columns can
be interpreted using this equation:
t
q
u C
L
q
u C
f L
B
app so
S o
app so
S o
A


t L
B

A plot of the breakpoint times, t
B
s at different
column heights, Ls, should give a straight line.
Remark: The parameter (
s app
q
so
) is more reliably
obtained from experiments than equilibrium data.
PIERO M. ARMENANTE
NJIT
Bohart and Adams Equation
Using a completely different approach Bohart and
Adams (1920) proposed an equation very similar
to the previous one:
t
q
u C
L
k C
C
C
B
s app so
S o r o
o
B

_
,

1
1 ln
which can also be used to interpret the
experimental data from test columns.
PIERO M. ARMENANTE
NJ IT
Interpretation of Experimental Data
from Test Columns of Different Lengths
0 10 20 30 40 50
t (days)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
C
/
C
o
Port 1
1.5 m
Port 2
3 m
Port 3
4.5 m
t
B
t
E
Port 1
Port 2
1.5 m
Port 3
PIERO M. ARMENANTE
NJIT
Interpretation of Experimental Data
from Test Columns of Different Lengths
Example of experimental data:
Height of
Column (m)
t
B
(days)
t
E
(days)
1.5 6.3 18.5
3 18.1 31.5
4.5 26.3 41.1
Port 1
Port 2
1.5 m
Port 3
PIERO M. ARMENANTE
NJIT
Interpretation of Experimental Data
from Test Columns of Different Lengths
0 1 2 3 4 5
Column Height, L, (m)
-10
0
10
20
30
40
50
t
B

o
r

t
E

(
d
a
y
s
)
Breakpoint
Exhaustion Point
Pollutant Concentration in Wastewater at Breakpoint = 10% C
o
Pollutant Concentration in Wastewater at Exhaustion Point = 90% C
o
(
s app
q
so
)/C
o
u
s
Approximate Height of
Adsorption Zone
PIERO M. ARMENANTE
NJIT
Design Method for BDST Method
Obtain experimental t
B
vs. L data at breakpoint
for columns of different depths. Possibly (but
not necessarily) use same flow velocity (u
S
) in
the experimental and in the full scale column;
Interpret the data using the expression for
t
B
=f(L) or the Bohart and Adams equation and
obtain equation parameters (
s app
q
so
and
intercept);
Determine service time (t
B
) for the a full scale
column of a fixed depth (or the column depth
for a given time).
PIERO M. ARMENANTE
NJIT
Determination of Moving-Bed
Adsorption Performance
The same equations that were used above for the
alternative determination of the adsorption zone
profile can be used also for sizing and
determining the pollutant removal efficiency of a
continuous moving bed adsorber in which carbon
is continuously added to the column.
PIERO M. ARMENANTE
NJIT
Monitoring of Adsorption Columns to
Detect Breakpoint
By monitoring the pollutant concentration in the
wastewater at different sampling ports along the
column the progression of the adsorption wave
can be monitored and the breakpoint anticipated
PIERO M. ARMENANTE
NJIT
Regeneration of Carbon Beds
Depending on the type of pollutant adsorbed on
the bed spent activated carbon beds can be
regenerated using two different methods, i.e.:
chemical regeneration
thermal regeneration
Thermal regeneration is by far the most common
method.
PIERO M. ARMENANTE
NJIT
Chemical Regeneration
Chemical regeneration relies on the use of
chemicals to produce dissolution or oxidation
of the adsorbate
Chemical regeneration agents that have been
used include:
- NaOH - NaOCl
- HCl - H
2
O
2
- CCl
4
Chemical regeneration is only partially
effective and is not as commonly used as
thermal regeneration
PIERO M. ARMENANTE
NJIT
Thermal Regeneration
Thermal regeneration consists of processing
the spent carbon at high temperature to
volatilize and/or burn the adsorbed materials.
Thermal regeneration typically involves some
loss of carbon (typically between 5 and 10%)
and some changes in the adsorption
characteristics of the carbon itself (mainly
caused by the reactivation process producing
larger pores than those present in the original
material).
Thermal regeneration can be conducted on
site or, more often, off-site.
PIERO M. ARMENANTE
NJIT
Thermal Regeneration
Thermal regeneration is typically conducted in
a furnace (e.g., rotary hearth, fluidized bed).
In those cases in which only or mainly volatile
compounds have been adsorbed on the bed
steam stripping can be effectively used at
temperature high enough to produce
volatilization of the adsorbate, but low enough
to minimize degradation of the activated
carbon. The stripped volatile organics can
then be condensed separately.
If non-volatile compounds are also present
they will stay in the carbon and accumulate.
PIERO M. ARMENANTE
NJIT
Thermal Regeneration
Thermal regeneration typically includes the
following steps:
Drying at 100 to 150
o
C (212 to 300
o
F) to
remove the water
Volatilization of the light organic compounds
at 150 to 315
o
C (300 to 600
o
F)
Pyrolysis of the heavier organic compounds at
temperatures as high as 800
o
C (1500
o
F)
Re-activation of the carbon at temperatures as
high as 1040
o
C (1900
o
F) in the presence of an
oxidizer (steam, carbon monoxide, or oxygen)
PIERO M. ARMENANTE
NJIT
Additional Information and Examples on Adsorption
Additional information and examples can be found
in the following references:
Corbitt, R. A. 1990, The Standard Handbook of
Environmental Engineering, McGraw-Hill, New
York, pp. 5.140-5.146; 6.195-6.202.
Droste, R. L., 1997, Theory and Practice of Water
and Wastewater Treatment, John Wiley & Sons,
New York, pp. 484-507.
Eckenfelder, W. W., Jr., 1989, Industrial Water
Pollution Control, McGraw-Hill, New York, pp.
263-284.
PIERO M. ARMENANTE
NJIT
Additional Information and Examples on Adsorption
Freeman, H. M. (ed.), 1989, Standard Handbook
of Hazardous Waste Treatment and Disposal,
McGraw-Hill, New York, pp. 6.3-6.21.
LaGrega, M. D., Buckingham, P. L., Evans, J. C.,
1994, Hazardous Waste Management, McGraw-
Hill, New York, pp. 476-486.
Metcalf & Eddy, 1991, Wastewater Engineering:
Treatment, Disposal, and Reuse, McGraw-Hill,
New York, pp. 314-324; 751-755.
Sundstrom, D. W. and Klei, H. E., 1979,
Wastewater Treatment, Prentice Hall, Englewood
Cliffs, NJ, pp. 241-273.
PIERO M. ARMENANTE
NJIT
Additional Information and Examples on Adsorption
Treybal, R. E., 1968, Mass Transfer Operation,
McGraw-Hill, New York, pp. 490-568.
Weber, W. J., Jr., 1972, Physicochemical Process
for Water Quality Control, Wiley-Interscience,
John Wiley & Sons, New York, pp. 199-259.
Wentz, C. W., 1995, Hazardous Waste
Management, Second Edition, McGraw-Hill, New
York, pp. 201-202.